Structured material and producing method thereof

ABSTRACT

A structured material characterized in having, on a substrate, a layer having tubular pores positioned uniaxially parallel to the interface of the substrate and the layer and supporting a conductive polymer material having a function of a surfactant therein. A method for producing the above structure material characterized by the steps of providing a substrate having the anisotropy on a surface, applying a solution containing a surfactant having a functional group for polymerization in the molecular structure, a solvent therefor, and a solute different from the surfactant to the substrate, and a step of standing for a predetermined time for causing the surfactant to assemble in a predetermined direction based on the anisotropy of the substrate.

This application claims priority from Japanese Patent Application No.2003-278340, filed on Jul. 23, 2003, which is hereby incorporated hereinby reference.

TECHNICAL FIELD

The present invention relates to a structured material including apolymer compound, and more particularly, to a technology for orientingchains of a polymer utilizing pore-orienting technology.

BACKGROUND ART

Conductive polymers are being actively investigated because of theirpotential in production of inexpensive organic transistors. Conductivepolymers have a structure in which a conjugated chain extends as a mainchain, and show a high conductivity in such a direction. However, suchconductive polymers are utilized in a bulk state because of the absenceof an effective technology for orienting main chains of the conductivepolymer, and sufficient electroconductivity is currently not obtainedbecause the conduction between the polymer chains is achieved by thehopping conduction. For orienting the polymer chains, investigations arebeing conducted, for example, utilizing a Langmuir-Blodgett film.

A structured material prepared by using molecular assemblies ofsurfactants as a template has a structure in which molecular assembliesof the surfactant are regularly arranged by self-organization in amatrix of an inorganic compound. Particularly, a structured materialhaving pores of an average diameter of 2 to 50 nm is called a mesoporousstructure, which is referred to as a mesostructured material in thepresent description. A structured material in which pores are filledwith a material is also called a mesostructured material. Initially, theinorganic compound was limited to silica, but such a structure can nowbe prepared with various materials such as oxides, metals or sulfides. Astructure in which pore walls are constituted of an inorganic-organicnanocomposite material is now also available. Also, the originally foundmaterial was in a powder state, but now various forms, such as a film, afiber, a sphere etc., are available.

The mesostructured material, by making it possible to introduce anothermaterial into regular nanospaces, thereby controlling structure ororientation of such material, is expected to be of use for applicationsin electronic materials and optical materials in addition toconventional applications of porous materials, such as anadsorption/separation material or a catalyst, and investigations arebeing conducted in a wide variety of fields. There are principally twomethods for introducing a material into the pores of a mesostructurematerial. One is to eliminate the surfactant assemblies constitutingpores and introduce a guest material into thus formed hollow pores. Thismethod is generally employed for mesoporous silica, but cannot beapplied to a material in which the mesostructure is damaged by theelimination of the surfactant assemblies. This method has a difficultyrelated to the introduction of a bulky guest species, such as a polymermaterial, when the structure is a film or the like. The other method isto make the guest species coexist during the preparation of amesostructured material, whereby the guest species is held in the poresat the time the mesostructured material is prepared. This method has anadvantage in that it is applicable to a wide range of mesostructurematerials since the surfactant need not be eliminated, but there is aconsiderable limitation as to the guest species that can be introducedby this method.

There recently has been reported a technology of forming a functionalmaterial in pores by a method other than the two methods mentionedabove. This method is based on providing the surfactant itself with afunctionality and preparing a mesostructured material having afunctional material in the pores without eliminating the surfactant.This method is applied to a film, or a fiber as described in AngewandteChemie, International Edition, 40, pp. 3803-3806, in which amesostructured material is prepared by using surfactants having apolymerizable functional group in the molecular structure and thenpolymerization is achieved by heat etc., thereby preparing conductivepolymer chains in the pore.

However, the aforementioned method of preparing a mesostructuredmaterial utilizing surfactants having a polymerizable functional groupin the molecular structure is difficult to practice because of thefollowing reasons.

In a film employed in prior technologies, tubular pores in the filmplane have random directions so that the polymer chains have randomdirections macroscopically even if a polymer chain is formed along thepore direction. On the other hand, a fibered structure is small anddifficult to handle, and also, as described in Advanced Materials, 12,pp 961-965, a pore formed a spiral in the fiber. Consequently, even ifthe polymer chain is oriented along the direction of the pore, thepolymer chain assumes a spiral form in this method so that it isdifficult to control the direction of the polymer chain by the pores.

On the other hand, Science, 288, pp 652-656 describes a partialorientation of a conductive polymer compound utilizing a mesostructuredsilica monolith in which pore direction is oriented by a strong magneticfield. This method eliminates the surfactant by calcination after thepreparation of a mesostructured silica and to introduce a conductivepolymer compound into thus formed hollow nanospace, but the obtainedmesostructured silica, having numberless fine cracks, is difficult toapply to an optical material or an electronic material, and an alignmentcontrol of conductive polymer main chains over the entire structure isnot achieved as the polymers present in such cracks are random.

The present invention is to achieve an orientation control of polymerchains on a macroscopic scale, utilizing a mesostructured film in whichtubular pores are oriented in one direction.

SUMMARY OF THE INVENTION

The present invention provides a structured material formed by a layerhaving tubular pores on a substrate, in which the tubular pores arepositioned parallel to the interface of the substrate and the layer, anda conductive polymer is held in the tubular pores.

The present invention also provides a production method for a structuredmaterial, which comprises the steps of: applying a solution containingsurfactants that has a polymerizable functional group in the molecularstructure, a solvent, and a solute different from the surfactants, ontoa substrate having anisotropy, and the step of leaving the product ofthe above step standing for a predetermined time for causing thesurfactant to assemble in a direction on the basis of the anisotropy ofthe substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of a mesostructured film prepared in thepresent invention including orienting conjugated polymer chains in thepores.

FIG. 2 is a schematic view of a mesostructured film beforepolymerization.

FIG. 3 is a schematic view showing an apparatus for preparing aLangmuir-Blodgett film to be employed in the present invention.

FIG. 4 is a schematic view showing a reaction vessel for preparing, inthe present invention, a mesostructured film having orienting tubularpores by heterogeneous nucleation and growth.

FIGS. 5A, 5B, 5C, 5D, and 5E show chemical structures of surfactantsadvantageously employed in the present invention.

FIG. 6 is an another schematic view of a mesostructured film prepared inthe present invention including orienting conjugated polymer chains inthe pores.

FIG. 7 is a schematic view showing a dip coating apparatus for preparinga film to be employed in the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

An oriented mesostructured film including a conjugated polymer in thepresent invention has a structure, for example, as schematically shownin FIG. 1. A mesostructured film 12 having tubular pores of a honeycombstructure is formed on a substrate 11 having a structural anisotropy atthe surface. In the mesostructured film, tubular mesopores 13 areoriented in one direction. In the pore, as illustrated, a conjugatedpolymer is formed by polymerization of surfactants. The presentinventors estimate that a single tubular pore contains plural conjugatedpolymer chains 14 (FIG. 1) or 21 (FIG. 6). The conjugated polymer chain14 indicates a polydiacetylene derivative, while the chain 21 indicatesa polypyrrole derivative.

The oriented mesostructured film including the conjugated polymer in thepresent invention is formed by causing a polymerization reaction of thesurfactant molecules in the pores formed by assemblies of surfactants 22having a polymerizable functional group as a template. The film beforepolymerization is also an embodiment of the present invention. Thesurfactant assemblies exist in a tubular formation in a compositematerial, and its cross section is schematically illustrated by 21 inFIG. 2.

In the following, there will be given detailed descriptions on methodsof producing an oriented mesostructured film of the present invention,including the conjugated polymer compound, and a detailed configurationthereof.

In configurations shown in FIGS. 1 and 2, the numeral 11 denotes asubstrate having a structural anisotropy on the surface. The substratehaving the surface anisotropy employable in the present inventiongenerally belongs in one of the following two categories. One is acrystalline substrate having a strong anisotropy in an atomicarrangement on the surface, and the other is an ordinary substrate, suchas glass, on the surface of which a material having a structuralanisotropy is provided.

The method of utilizing a crystalline substrate having a stronganisotropy in the atomic arrangement on the surface requires the use ofa relatively expensive monocrystalline substrate. However, there is anadvantage in that a mesostructured material having oriented tubularpores can be directly formed on the substrate. In such a case, when aconductive monocrystalline substrate is used, a satisfactory electriccontact between the substrate and the conductive polymer in the pore isexpected. A preferable crystalline substrate with a strong anisotropy inthe atomic arrangement is a substrate the surface atomic arrangement ofwhich shows a twofold symmetry. On the surface of such a crystallinesubstrate, the direction of a specified arrangement of atoms is uniquelydetermined, thereby realizing an ability of orienting the surfactantassemblies. There is preferably employed a single crystal substratehaving a diamond-like crystal structure or the (110) plane of a singlecrystal substrate of a sphalerite-like crystal structure, particularlythe (110) plane of silicon.

A method of forming a material having a structural anisotropy on asurface of an ordinary substrate, though involving an extremely thinlayer between the substrate and the mesostructured material, has anadvantage of achieving a highly uniaxial orienting property with aninexpensive material. As a material having a structural anisotropy onthe surface of the substrate, there is advantageously employed aLangmuir-Blodgett film of a polymer or a polymer film subjected to arubbing process.

First, a method for preparing a substrate will be explained.

When a crystalline substrate having a surface atomic arrangement with atwofold symmetry is used for preparation of a mesostructured material,the substrate is sufficiently washed to expose a clean crystal surface.Then, for example, in a case of a silicon substrate, a spontaneous oxidefilm on the surface is eliminated. This can be achieved by a simpleprocess, for example, by treating the surface with diluted hydrofluoricacid for several minutes. A substrate with a crystal surface exposed bysuch treatment can be directly employed in the preparation of amesostructured film, which is discussed below.

Then a case where a material having a structural anisotropy is formed ona surface of an ordinary substrate will be explained.

First, there will be explained a method of forming a Langmuir-Blodgettfilm (LB film) of a polymer compound. The LB film is formed bytransferring a monomolecular film, developed on a water surface, ontothe substrate, and can be formed as a film of a desired number of layersby repeating this film formation. The term LB film used in the presentinvention includes laminated monomolecular films of an LB filmderivative, formed by a heat treatment or the like, to an LB film formedon the substrate to modify the chemical structure while maintaining thelaminated structure.

The LB film can be prepared by an ordinary method. An ordinary LB filmforming apparatus is schematically shown in FIG. 3. In FIG. 3, there areshown a tank 31 filled with pure water 32, and a fixed barrier 33 with asurface pressure sensor (not shown). A monomolecular film 36 on thewater surface is formed by dropping a liquid, in which a desiredsubstance or a precursor of a desired substance is dissolved, onto thewater surface in an area between the barrier 33 and a movable barrier34. A surface pressure is applied to the film by a movement of themovable barrier 34. The movable barrier is position-controlled by thesurface pressure sensor in such a manner that a constant surfacepressure is applied during the film formation on the substrate. The purewater is maintained in a clean state by a water supply apparatus and awater discharge apparatus (not shown). The water tank 32 is providedwith a hole, at which position a substrate 35 is held to be movedvertically at a constant speed by a translation movement device (notshown). The film on the water surface is taken up onto the substratewhen it is immersed into water or extracted therefrom.

The LB film employed in the present invention is formed on the substrateas a monomolecular layer at a time, by applying a surface pressure to amonomolecular layer formed on the water surface in the aforementionedapparatus and immersing and extracting the substrate into and from thewater. The form and properties of the film are controlled by the surfacepressure, the moving speed of the substrate in immersion/extraction, andthe layer number. The optimum surface pressure for the film formation isdetermined according to a surface area-surface pressure curve, but isgenerally within a range from several to several tens of mN/m. Also themoving speed of the substrate is generally within a range from severalto several hundred mm/min. The number of layers is suitably determinedwithin a range from several layers to several hundred layers. The LBfilm formation is generally prepared by the aforementioned method, butit is not limited thereto, and there can also be employed, for example,a method utilizing a flow of water constituting a sub-phase.

A material constituting the LB film is not particularly limited as longas it can withstand a process for forming a mesostructured filmdiscussed below and is capable of controlling uniaxial orientation ofthe pores in the mesostructure, and, for example, a polyimide can beadvantageously employed.

In the following, there will be explained a method of utilizing asubstrate bearing a polymer film subjected to a rubbing process. Therubbing process is a method of coating a polymer on the substrate, forexample, by spin coating, and rubbing such coating with a cloth or thelike. The rubbing cloth is wound on a roller, and the rubbing isconducted by contacting the rotating roller with the surface of thesubstrate and moving a stage supporting the substrate in a directionwith respect to the roller.

The rubbing cloth is optimally selected according to the polymermaterial to be used, but can be an ordinary material, such as nylon orrayon. The rubbing intensity is optimized by parameters, such as therevolution of the roller, pressure of the roller to the substrate, andthe moving speed of the stage supporting the substrate.

In the following, a method for forming a mesostructured film on thesubstrate will be explained. The method for forming a mesostructuredfilm on the substrate is classified largely into two categories. One isbased on heterogeneous nucleation and growth from a solution to asurface of a substrate, while the other being based on a sol-gel method.

First, a method based on heterogeneous nucleation and growth occurringat the solid-liquid interface will be explained. This method isprincipally used for preparing a mesostructured silica film by a processsimilar to crystal growth. In this method, an aforementioned substrateis maintained in a precursor solution containing a raw material for adesired pore wall constituting material in an aqueous solution ofsurfactants, whereby a mesostructured film is formed on the substrate.

A reaction vessel to be used for the formation of the mesostructuredfilm, for example, has a structure as shown in FIG. 4. The materialconstituting the reaction vessel 41 is not particularly limited as longas it does not affect the reaction, and can be, for example,polypropylene or Teflon (registered trade name). The reaction vessel maybe placed in a closed container of a highly rigid material, such asstainless steel, in order for it not to be damaged even if pressure isapplied during the reaction. In the reaction vessel, a substrate holder43 is provided as shown in FIG. 4 for supporting a substrate 45. Duringthe reaction, the formation of the mesostructured material takes placenot only on the substrate, but also in the solution, so that aprecipitate in the solution is deposited onto the substrate. In order toprevent such a situation, the substrate is held facing down, i.e., withthe film forming surface downward, in the solution during the reaction.

The reaction solution is formed by adding an acid etc., to an aqueoussolution of surfactants for regulating the pH so that it is suitable forthe formation of a desired pore wall, and adding a raw materialsubstance, such as an alkoxide, for a desired material. A preferablealkoxide is one that generates water-soluble alcohol by hydrolysis.

The surfactant to be employed is provided, in the molecular structure,with a functional group capable of forming a conjugated polymer bypolymerization, and is preferably a cationic surfactant having ammoniumas a hydrophilic group, as indicated by FIG. 5B, 5D or 5E, or a nonionicsurfactant having polyethylene oxide as a hydrophilic group, asindicated by FIG. 5A or 5C.

However, the usable surfactant is not limited to these. Also, the lengthof a hydrophobic group and the size of a hydrophilic group in thesurfactant molecule are determined according to the pore size of adesired mesostructure. The position of the polymerizable functionalgroup in the molecular structure is so determined as to do an optimumpolymerization behavior.

The functional group capable of forming a polymer compound bypolymerization is preferably a diacetylene group, a pyrrole group, athiophene group etc., and a surfactant containing such a group in thestructure can provide polydiacetylene, polypyrrole, polythiophene etc.,as discussed below. However, the functional group capable of forming apolymer compound applicable in the present invention and the formedpolymer compound are not limited to the foregoing examples, and anyconjugated polymer compound that can be formed by polymerization in thepore may be employed.

In the present invention, the aforementioned substrate having thestructural anisotropy on a surface is placed in the above-explainedprecursor solution and is maintained for 1 to 10 days at a temperatureoptimized for the compound constituting the desired pore wall, whereby amesostructured film having tubular pores in a controlled direction isformed on the substrate. The film thickness can be controlled, forexample, by the reaction time. In such a mesostructured material, theassemblies of surfactants having a polymerizable functional group in themolecular structure constitute a template for the tubular pore.

In the following, a method based on a sol-gel process will be explained.It is a simple method applicable to the preparation of a mesostructuredfilm of various materials, and involves coating a precursor solution,containing surfactants and a pore wall raw material, on a substrate,evaporating the solvents, hydrolysis and condensation.

The precursor solution employed in this method is formed by adding a rawmaterial for the pore wall constituting material to a solution ofsurfactants. For the solvent, an alcohol, such as ethanol orisopropanol, is advantageously employed, but this is not restrictiveand, for example, a mixture of alcohol and water or water may be useddepending on the desired pore wall material.

The raw material for the pore wall is not particularly limited as longas it can form the desired material by hydrolysis, and canadvantageously be a metal halide or an alkoxide, particularly preferablytin chloride, tin alkoxide, titanium chloride, titanium alkoxide,silicon chloride or silicon alkoxide.

The surfactant to be employed includes in its molecular structure, as inthe case of the method based on heterogeneous nucleation and growth, afunctional group capable of polymerization to form a conjugated polymer.In this method, there are preferably employed surfactants includingpolyethylene oxide as a hydrophilic group. Therefore, among thestructures shown in FIGS. 5A to 5E, those indicated by FIGS. 5A and 5Care usable. However, the usable surfactant is not limited to suchstructures. Also, in the surfactant molecule to be used, a length of ahydrophobic group and a size of a hydrophilic group are determinedaccording to pore size of a desired mesostructured material. Theposition of the polymerizable functional group in the molecularstructure is determined so as to achieve an optimum polymerizationbehavior.

The precursor solution of the above-described composition is applied onthe aforementioned substrate having the anisotropy, or placed on anarbitrary position thereon. The coating can be achieved by variousmethods, such as dip coating, spin coating or mist coating. Othercoating methods capable of uniform coating are also applicable. Anapparatus for spin coating or dip coating can be an ordinary one withoutany particular restriction, but means for controlling the temperature ofthe solution and means for controlling temperature and humidity of theatmosphere for coating may be provided in certain cases.

As an example, a method for producing a mesostructured thin filmutilizing dip coating will be explained. An example of the apparatusused for dip coating is illustrated in FIG. 7, in which a container 71,a substrate 72, and a precursor solution 73 are shown.

A substrate to be subjected to the formation of a mesostructured film isfixed by a substrate holder 74 to a rod 75 and is vertically moved by az-stage 76. The direction of anisotropy of the substrate may bearbitrarily selected with respect to the direction of dip coating.

At the film formation, the precursor solution 73 is heated to a desiredtemperature, utilizing a heater 78 and a thermocouple 77, if necessary.In order to improve the control of the solution temperature, the entirecontainer may be placed in a heat insulating container (not shown). Thethickness of the film can be controlled by varying coating conditions.

Also, for positioning the precursor solution in an arbitrary position onthe substrate, various methods can be employed, such as a micro-contactprinting method, an ink jet method or a pen lithography method. Thesemethods allow to pattern the mesostructured film at a desired positionon the substrate.

The substrate coated with the solution is dried by evaporating thesolvent in an atmosphere from room temperature to about 60° C. Then, ifnecessary, it is exposed to water vapor by holding the substrate in ahigh temperature atmosphere. The inventors estimate that, in thesedrying and vapor exposure steps, tubular assemblies of the surfactantsare subjected to a structural anisotropy of the substrate whereby thepores are uniaxially orientated.

Through the method explained in the foregoing, a mesostructured film isobtained in which assemblies of the surfactants, having a polymerizablegroup in the molecular structure, are included in tubular pores. Thisfilm is defined as a precursor film for an oriented mesostructured filmincluding a conjugated polymer, and is explained in the following.

The precursor mesostructured film prepared as explained above issubjected to thermal or light stimulation to polymerize the surfactantmolecules present in each pore, thereby forming a polymer compound inthe pore. A surfactant having a diacetylene group in the molecularstructure allows to obtain a conjugated polymer polydiacetylene in thepore.

Polydiacetylene can be confirmed by infrared absorption spectroscopy andfluorescence spectroscopy, and the orientation of the polymer main chainin the pore can be confirmed by measuring polarized light via absorptionspectroscopy and light emission spectroscopy.

In the following, the present invention will be further clarified byexamples.

Example 1

In this example, a mesostructured silica film including uniaxiallyoriented tubular pores on a substrate was formed by employing asubstrate subjected to a rubbing process, a cationic surfactantcontaining a diacetylene group and a heterogeneous nucleation/growth.Thermal polymerization of the surfactants was carried out in theoriented pores thereby forming a conjugated polymer compound having anoriented polymer chain.

A silica glass substrate was rinsed with acetone, isopropyl alcohol andpure water and subjected to surface cleaning in an ozone generatingapparatus, spin-coated with an NMP solution of polyamic acid and bakedfor 1 hour at 200° C. to convert to polyimide A coating of the followingstructure:

It was then subjected to a rubbing process under conditions shown inTable 1 to obtain a substrate.

TABLE 1 Cloth material Nylon Roller diameter (mm) 24 Press-in amount(mm) 0.4 Revolution (rpm) 1,000 Stage speed (mm/min) 600 Number ofrepetition 2

On this substrate, a mesostructured silica film was formed utilizingsurfactants that have a polymerizable group in the molecular structure.

The cationic surfactant A employed in the present invention has thefollowing molecular structure:CH₃(CH₂)₁₀—C≡C—C≡C—CH₂—N⁺(CH₃)₃Br⁻

0.36 g of the surfactant A was dissolved in 12.8 ml of pure water, and6.8 ml of concentrated hydrochloric acid (36%) was added. Then, 0.28 mlof tetraethoxysilane was added and the mixture was stirred for 3minutes.

The substrate with the rubbing-treated polyimide was held in thisreactant solution with the polyimide surface facing down, and then thevessel containing the reaction solution was sealed at 80° C. for 3 daysfor the formation of a mesostructured silica film. In order to achieve asatisfactory uniaxial alignment of the mesopores in the mesostructuredsilica film, the surface was covered with another silica glass plateusing a spacer during the reaction. The reaction vessel employed was asschematically shown in FIG. 4.

The substrate in the reactant solution for the predetermined time wastaken out from the vessel and rinsed sufficiently with pure water anddried at the room temperature in an ambient atmosphere. On thesubstrate, there was formed a continuous mesostructured silica film,which showed, when observed via an optical microscope, uniaxiallyoriented textures in a direction perpendicular to the rubbing direction,thereby suggesting an orientation of the pore.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of hexagonal porous structurescorresponding to a plane interval of 3.56 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of the uniaxial orientation of the tubularpores in this mesostructured silica film, this film was analyzed byin-plane X-ray diffraction. This method measures the in-plane rotationaldependence of the X-ray diffraction intensity resulting from the (110)plane perpendicular to the substrate, as described in Chemistry ofMaterial, vol. 12, p. 49, and can determine the orienting direction ofthe pores and its distribution. The in-plane rotation angle dependenceof the diffraction intensity on the (110) plane, measured in the presentexample, indicated that the pores in the mesostructured silica filmprepared in the present example were oriented perpendicular to therubbing direction of the polyimide film, and the distribution of theorientation direction was about 12° from the full width of the halfmaximum of the diffraction peak in the in-plane rocking curve.

Based on the foregoing, it is shown that a mesostructured silica filmhaving tubular pores of a uniaxial orientation can be formed on asubstrate with a rubbing-treated polyimide film, utilizing surfactantscontaining a polymerizable diacetylene group as a hydrophobic group.

Such a mesostructured film was heated for 3 hours at 170° C. in anitrogen gas atmosphere to polymerize the diacetylene group of thesurfactants. Infrared absorption spectroscopy of the mesostructured filmwas performed by an ATR method before and after heating. As a result, astrong absorption band of an acetylene bond at 2,260 cm⁻¹ observedbefore heating vanished after the heating, while other peaks did notshow a change. This result confirmed that the polymerization took placewithout decomposition of the surfactant molecules. Also, fluorescence,which was not observed in the film before heating, was observed in thefilm after heating, thus confirming formation of polydiacetylene in thepores. An investigation of the polarizing characteristics of theobserved fluorescence indicated that the polarization direction offluorescence was confirmed to be perpendicular to the rubbing direction,namely along the direction of the oriented pores, thereby confirmingorientation control of the polymer chains in the pores and orientationcontrol of the conjugated polymer chains on a macroscopic scale.

Example 2

In this example, a uniaxially oriented mesostructured film was preparedby employing the same surfactant A as in Example 1 and the silicon (110)single crystal substrate to form polydiacetylene in the oriented pores.

The same reactant solution and the vessel were used for preparing themesostructured silica as in Example 1.

The substrate was p-type Si (110) polished on one side and having aspecific resistance of 100 Ωcm. It was cut into a size of 2×2 cm, thentreated with a 1% solution of hydrofluoric acid for eliminating thespontaneous oxide film on the surface before use. The elimination of theoxide film can be confirmed by a fact that the surface of the siliconwafer becomes hydrophobic after the film elimination. After thisprocess, the substrate was sufficiently rinsed with pure water, held bya substrate holder with the polished surface facing down, and placed ina reactant solution in a Teflon (registered trade name) vessel. Thevessel was sealed for 3 days at 80° C. for the formation of amesostructured silica film.

The substrate, which was in the reactant solution for a predeterminedperiod of time, was taken out from the vessel and rinsed sufficientlywith pure water and dried at room temperature. A continuousmesostructured silica film was formed on the substrate. Observation byan optical microscope showed uniaxially oriented textures, suggesting anorientation of the pore.

X-ray diffraction analysis of this film confirmed, as in Example 1, astrong diffraction peak assigned to the (100) plane of hexagonal porousstructures corresponding to a plane interval of 3.56 nm, therebyconfirming that the film had a pore structure in which tubular pores arehexagonally packed.

The uniaxial orientation of the tubular pores in this mesostructuredsilica film was analyzed by the in-plane X-ray diffraction as inExample 1. As a result, the distribution of orientation direction in thefilm prepared in the present example was about 29° from the full widthof the half maximum of the diffraction peak in the in-plane rockingcurve.

Based on the foregoing, it was shown that a mesostructured silica filmhaving tubular pores of an uniaxial orientation was formed on thesilicon (110) plane, utilizing surfactants containing a polymerizablediacetylene group as a hydrophobic group. The distribution oforientation of the pores in the mesostructured film of this example iswider than that in the film prepared in Example 1, but has advantages inthat a rubbing-treated step is unnecessary and the film can be prepareddirectly on the conductive substrate.

This mesostructured film was irradiated for 4 hours with an ultravioletlight at 254 nm by using a high pressure mercury lamp. Infraredabsorption spectroscopy of the mesostructured film was performed by anATR method before and after irradiation. As a result, a strongabsorption band of an acetylene bond at 2,260 cm⁻¹ observed beforeirradiation decreased in intensity after the irradiation, while otherpeaks did not show a change. This result confirmed that thepolymerization took place without decomposition of the surfactantmolecules. Also, fluorescence, which was not observed in the film beforeirradiation, was observed in the film after the irradiation, thusconfirming formation of polydiacetylene in the pores. An investigationof the polarizing characteristics of the observed fluorescence indicatedthat the polarization direction of fluorescence was confirmed along the<001> direction of the Si substrate, namely along the direction of theoriented pores, thereby confirming orientation control of the polymerchain in the pores and orientation control of the conjugated polymerchains on a macroscopic scale.

While it is possible that photopolymerization, which was utilized in thepresent example, can result in an incomplete polymerization, as shown bythe infrared absorption spectroscopy, it has an advantage in that aportion of polymerization can be patterned by light irradiation througha mask.

Example 3

In this example, a uniaxially oriented mesostructured film was preparedby employing the same surfactant A as in Examples 1 and 2, a silicaglass substrate coating a Langmuir-Blodgett film, and polydiacetylenewas prepared in the oriented pores. A Langmuir-Blodgett film wasprepared with a polyimide used in Example 1, and the same reactantsolution and vessel were used as in Examples 1 and 2.

Polyamic acid A and N,N-dimethylhexadecylamine were mixed in a 1:2 molarratio to obtain an N,N-dimethylhexadecylamine salt of polyamic acid A.It was dissolved in N,N-dimethylacetamide to obtain a 0.5 mM solution,which was dropped onto the surface of water in an LB film formingapparatus, maintained at 20° C. A monomolecular film formed on the watersurface was transferred onto the substrate with a dipping speed of 5.4mm/min under a constant surface pressure of 30 mN/m.

The substrate was a silica glass substrate rinsed with acetone,isopropyl alcohol and pure water, then subjected to surface cleaning inan ozone generating apparatus, and a hydrophobic treatment.

Thirty layers of LB films of polyamic acid alkylamine salt were formedon the substrate and baked for 30 minutes at 300° C. to convert topolyimide A. An imidization by dehydration ring-closing of polyamic acidand liberation of an alkylamine were confirmed by infrared absorptionspectroscopy. An orientation of the polymer chain in thus formedpolyimide LB film was analyzed by dichroic properties of infraredabsorption spectroscopy and was confirmed to be parallel to anextracting direction of the substrate at the LB film formation.

The same surfactant A containing a diacetylene group in the molecularstructure as in Examples 1 and 2 was employed to prepare a precursorsolution of the same composition as in Examples 1 and 2. The substratecoating the aforementioned layered LB film was supported in thissolution with the film-coating surface facing downs, and then the vesselcontaining the reactant solution was sealed for 3 days at 80° C. for theformation of a mesostructured silica film. In order to achieve thesatisfactory uniaxial alignment of the pores in the mesostructuredsilica film, the surface was covered with another silica glass plateusing a spacer during the reaction.

The substrate, which was in the reactant solution for a predeterminedperiod of time, was taken out from the vessel and rinsed sufficientlywith pure water and was dried at room temperature. On the substrate,there was formed a continuous mesostructured silica film, which showed,in observations by an optical microscope, a uniaxially oriented texturein a direction perpendicular to the extracting direction of thesubstrate, thereby suggesting an orientation of the pore.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of the hexagonal porous structurecorresponding to a plane interval of 3.60 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of the uniaxial orientation of the tubularpores in this mesostructured silica film, the film was analyzed byin-plane X-ray diffraction. As a result, it was indicated that thealignment of the pores in the prepared film was oriented perpendicularto the extracting direction of the substrate and the distribution of theorientation direction was about 15° from the full width of the halfmaximum of the diffraction peak in the in-plane rocking curve.

Based on the foregoing, it was shown that a mesostructured silica filmhaving tubular pores of a uniaxial orientation was formed on thesubstrate coating a polyimide LB film, utilizing surfactants containinga polymerizable diacetylene group as a hydrophobic group.

The above mesostructured film was heated for 3 hours at 170° C. in anitrogen gas atmosphere to polymerize the diacetylene group of thesurfactant. Infrared absorption spectroscopy of the mesostructured filmwas performed by an ATR method before and after heating. As a result, astrong absorption band of an acetylene bond at 2,260 cm⁻¹ observedbefore heating vanished after the heating, while other peaks did notshow a change. This result confirmed that the polymerization took placewithout decomposition of the surfactant molecules. Also, fluorescence,which was not observed in the film before heating, was observed in thefilm after the heating, thus confirming formation of polydiacetylene inthe pores. An investigation of the polarizing characteristics of theobserved fluorescence indicated that the polarization direction offluorescence was confirmed to be perpendicular to the extractingdirection of the substrate, namely along the orientation direction ofthe pores, thereby confirming orientation control of the polymer chainin the pores and orientation control of the conjugated polymer chains ona macroscopic scale.

Example 4

In this example, a uniaxially oriented mesostructured film in whichtubular pores were oriented in a direction and in which a pore wall wasconstituted of inorganic-organic nanocomposites was prepared byemploying a substrate with the rubbing-treated polyimide film as inExample 1, the same surfactant A as in Examples 1 to 3, and a precursor(silicon alkoxide A) represented by the following structural formulainstead of the silicon alkoxide employed in Examples 1 to 3, and aconjugated polymer chain was polymerized in the pores.

0.36 g of the surfactant A was dissolved in 12.8 ml of pure water, and3.8 ml of concentrated hydrochloric acid (36%) was added. Then, 0.50 gof the aforementioned silicon alkoxide A was added and the mixture wasstirred for 3 minutes.

The substrate with rubbing-treated polyimide was supported in thisreactant solution with the polyimide surface facing down, and then thevessel containing the reactant solution was sealed for 3 days at 70° C.for the formation of a mesostructured silica film. In order to achievethe satisfactory uniaxial alignment of the pores in the mesostructuredsilica film, the surface was covered with another silica glass plateusing a spacer during the reaction.

The substrate, which was in the reactant solution for a predeterminedperiod of time, was taken out from the vessel and rinsed sufficientlywith pure water and dried at room temperature in an ambient atmosphere.On the substrate, there was formed a continuous mesostructured silicafilm, which showed, when observed through an optical microscope, auniaxially oriented texture in a direction perpendicular to the rubbingdirection, thereby suggesting an orientation of the pore.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of hexagonal porous structurescorresponding to a plane interval of 3.48 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of the uniaxial orientation of the tubularpores in this mesostructured silica film, the film was analyzed byin-plane X-ray diffraction. As a result, it was indicated that the poresin the mesostructured silica film prepared in the present example wereoriented perpendicular to the rubbing direction of the polyimide, andthe distribution of the orientation direction was about 14° from thefull width of the half maximum of the diffraction peak in the in-planerocking curve.

Based on the foregoing, it was shown that a mesostructured silica filmhaving tubular pores of a uniaxial orientation, in which the pore wallwas constituted of a silica-organic hybrid material, was formed on asubstrate with the rubbing-treated polyimide film, utilizing surfactantscontaining a polymerizable diacetylene group as a hydrophobic group.

The above mesostructured film was heated for 3 hours at 170° C. in anitrogen gas atmosphere to polymerize the diacetylene group of thesurfactant. Infrared absorption spectroscopy of the mesostructured filmwas performed by an ATR method before and after heating. As a result, astrong absorption band of an acetylene bond at 2,260 cm⁻¹ observedbefore heating vanished after the heating, while other peaks did notshow a change. This result confirmed that the polymerization took placewithout decomposition of the surfactant molecules and the organiccomponent in the pore wall. Also, fluorescence, which was not observedin the film before heating, was observed in the film after the heating,thus confirming formation of polydiacetylene in the pore. Aninvestigation of the polarizing characteristics of the observedfluorescence indicated that the polarization direction of fluorescencewas confirmed to be perpendicular to the rubbing direction, namely alongthe direction of the oriented pores, thereby confirming orientationcontrol of the polymer chain in the pores and orientation control of theconjugated polymer chains on a macroscopic scale.

Example 5

In this example, a mesostructured tin oxide film having uniaxiallyoriented tubular pores was prepared by a sol-gel method (dip coating) onthe rubbing-treated substrate and by employing a nonionic surfactanthaving a diacetylene group. The surfactant was thermally polymerized inthe pores to form oriented polymer chains of a conjugated polymer.

The nonionic surfactant B employed in the present example had thefollowing structure:CH₃(CH₂)₁₁—C≡C—C≡C—(CH₂)₈—COO(CH₂CH₂O)₅H

2.0 g of the nonionic surfactant B was dissolved in 20 g of ethanol, and5.2 g of tin tetrachloride was added.

A silica glass substrate with rubbing-treated polyimide film wasprepared in the same manner as in Example 1. The mesostructured tinoxide film was prepared by dip coating with the above solution and driedin an environment at a temperature of 40° C. and a relative humidity of20%. The direction of dip coating was parallel or perpendicular to therubbing direction of the substrate.

After drying for 10 hours, the film was maintained for 40 hours in anenvironment at a temperature of 40° C. and a relative humidity of 80%,and the relative humidity was then reduced to 20%. The obtained film wascompletely transparent.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of hexagonal porous structurescorresponding to a plane interval of 4.60 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of the uniaxial orientation of the tubularpores in this mesostructured tin oxide film, the film was analyzed byin-plane X-ray diffraction. As a result, it was indicated that the poresin the prepared film were oriented parallel to the rubbing direction,and the distribution of the orientation direction was about 15° from thefull width of the half maximum of the diffraction peak in the in-planerocking curve.

No difference was observed in the orientation state between the films inwhich the dip coating direction was parallel or perpendicular to therubbing direction of the polyimide film, showing that the observedorientation of the tubular pores was restricted by the anisotropy of thesubstrate.

The above mesostructured tin oxide film was heated for 3 hours at 170°C. in a nitrogen gas atmosphere to polymerize the diacetylene group ofthe surfactant. It was indicated by X-ray diffraction analysis that thepore structure shrank during a period thereof, but retained thestructure by heating. Infrared absorption spectroscopy of themesostructured film was performed by an ATR method before and afterheating. As a result, a strong absorption band of an acetylene bond at2,260 cm⁻¹ observed before heating vanished after the heating, whileother peaks did not show a change. This result confirmed that thepolymerization of the surfactant molecules took place withoutdecomposition of the surfactant molecules. Also, fluorescence, which wasnot observed in the film before heating, was observed in the film afterthe heating, thus confirming formation of polydiacetylene in the pores.An investigation of the polarizing characteristics of the observedfluorescence indicated that the polarization direction of fluorescencewas confirmed to be parallel to the rubbing direction, namely along thedirection of the oriented pores, thereby confirming orientation controlof the polymer chain in the pores and orientation control of theconjugated polymer chains on a macroscopic scale.

Example 6

In this example, a mesostructured titanium oxide film having uniaxiallyoriented tubular pores was prepared by a sol-gel (dip coating) method onthe rubbing-treated substrate by employing a nonionic surfactant havinga diacetylene group, and the surfactant was thermally polymerized in thepores to form oriented polymer chains of a conjugated polymer.

The same nonionic surfactant B was employed in the present example as inExample 5.

2.0 g of the nonionic surfactant B was dissolved in 20 g of ethanol, and3.8 g of titanium tetrachloride was added.

A silica glass substrate with rubbing-treated polyimide film wasprepared in the same manner as in Example 1. The mesostructured titaniumoxide film was prepared by dip coating with the above solution, anddried in an environment at a temperature of 40° C. and a relativehumidity of 20%. The direction of dip coating was parallel orperpendicular to the rubbing direction of the substrate.

After drying for 10 hours, the film was maintained for 1 hour in anenvironment at a temperature of 40° C. and a relative humidity of 80%,and the relative humidity was then reduced to 20%. The obtained film wascompletely transparent.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of hexagonal porous structurescorresponding to a plane interval of 4.56 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of uniaxial orientation of the tubularpores in this mesostructured titanium oxide film, the film was analyzedby in-plane X-ray diffraction. As a result, it was indicated that thepores in the prepared film were oriented parallel to the rubbingdirection, and the distribution of the orientation direction was about16° from the full width of the half maximum of the diffraction peak inthe in-plane rocking curve.

No difference was observed in the orientation state between the films inwhich the dip coating direction was parallel or perpendicular to therubbing direction of the polyimide film, showing that the observedorientation of the tubular pores was restricted by the anisotropy of thesubstrate.

The above mesostructured titanium oxide film was heated for 3 hours at170° C. in a nitrogen gas atmosphere to polymerize the diacetylene groupof the surfactant. The X-ray diffraction analysis showed that althoughthe period of the pore structures shrank by heating, the pore structurewas maintained. Infrared absorption spectroscopy of the mesostructuredfilm was performed by an ATR method before and after heating. As aresult, a strong absorption band of an acetylene bond at 2,260 cm⁻¹observed before heating vanished after the heating, while other peaksdid not show a change. This result confirmed that the polymerization ofthe surfactant molecules took place without decomposition of thesurfactant molecules. Also, fluorescence, which was not observed in thefilm before heating, was observed in the film after the heating, thusconfirming formation of polydiacetylene in the pores. An investigationof the polarizing characteristics of the observed fluorescence indicatedthat the polarization direction of fluorescence was confirmed to beparallel to the rubbing direction, namely along the direction of theoriented pores, thereby confirming orientation control of the polymerchain in the pores and orientation control of the conjugated polymerchains on a macroscopic scale.

Example 7

In this example, a mesostructured silica film having uniaxially orientedtubular pores was prepared by a sol-gel (dip coating) method on therubbing-treated substrate as in Example 1 and the surfactant A employedin Examples 1 to 4, and the surfactant was thermally polymerized in thepores to form oriented polymer chains of a conjugated polymer.

1.6 g of the cationic surfactant A was dissolved in 20 g of ethanol, and4.2 g of tetraethoxysilane was added. 0.27 g of water and 0.8 g of 0.1 Mhydrochloric acid were added to this solution and stirred for 2 hours.

This solution was applied on the rubbing-treated substrate by dipcoating and dried in an environment at a temperature of 25° C. and arelative humidity of 50%. The dip coating direction was parallel orperpendicular to the rubbing direction of the substrate. The obtainedfilm was completely transparent.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of hexagonal porous structurescorresponding to a plane interval of 4.08 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of the uniaxial orientation of the tubularpores in this mesostructured silica film, this film was analyzed byin-plane X-ray diffraction. As a result, it was indicated that the poresin the prepared film were oriented perpendicular to the rubbingdirection, and the distribution of the orientation direction was about8° from the full width of the half maximum of the diffraction peak inthe in-plane rocking curve.

No difference was observed in the orientation state between the films inwhich dip coating direction was parallel or perpendicular to the rubbingdirection of the polyimide film, showing that the observed orientationof the tubular pores was restricted by the anisotropy of the substrate.

Based on the foregoing, it was shown that a mesostructured silica filmhaving tubular pores of a uniaxial orientation was formed on the rubbingtreated substrate, utilizing surfactants containing a polymerizablediacetylene group as a hydrophobic group.

The above mesostructured film was heated for 3 hours at 170° C. in anitrogen gas atmosphere to polymerize the diacetylene group of thesurfactant. Infrared absorption spectroscopy of the mesostructured filmwas performed by an ATR method before and after heating. As a result, astrong absorption band of an acetylene bond at 2,260 cm⁻¹ observedbefore heating vanished after the heating, while other peaks did notshow a change. This result confirmed that the polymerization of thesurfactant molecules took place without decomposition of the surfactantmolecules. Also, fluorescence, which was not observed in the film beforeheating, was observed in the film after the heating, thus confirmingformation of polydiacetylene in the pores. An investigation of thepolarizing characteristics of the observed fluorescence indicated thatthe polarization direction of fluorescence was confirmed to beperpendicular to the rubbing direction, namely along the direction ofthe oriented pores, thereby confirming orientation control of thepolymer chain in the pores and orientation control of the conjugatedpolymer chains on a macroscopic scale.

Example 8

In this example, a mesostructured silica film having uniaxially orientedtubular pores was prepared by a sol-gel (dip coating) method on therubbing-treated substrate as in Example 1 and a cationic surfactantcontaining a thiophene group, and the surfactant was subjected to achemical oxidation polymerization in the pores to form oriented polymerchains of a conjugated polymer.

A cationic surfactant E employed in the present example had a structureshown in FIG. 5E.

2.3 g of the cationic surfactant E was dissolved in 20 g of ethanol, and4.2 g of tetraethoxysilane was added. 0.27 g of water and 0.8 g of 0.1 Mhydrochloric acid were added to this solution and stirred for 2 hours toobtain a precursor solution.

This solution was applied on the rubbing-treated substrate by dipcoating and dried in an environment at a temperature of 25° C. and arelative humidity of 50%. The dip coating direction was parallel orperpendicular to the rubbing direction of the substrate. The obtainedfilm was completely transparent.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of hexagonal porous structurescorresponding to a plane interval of 4.12 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of the uniaxial orientation of the tubularpores in this mesostructured silica film, this film was analyzed byin-plane X-ray diffraction. As a result, it was indicated that the poresin the prepared film were oriented perpendicular to the rubbingdirection.

No difference was observed in the orientation state between the films inwhich dip coating direction was parallel or perpendicular to the rubbingdirection of the polyimide film, showing that the observed orientationof the tubular pores was restricted by the anisotropy of the substrate.

Based on the foregoing, it was shown that a mesostructured silica filmhaving tubular pores of a uniaxial orientation was formed on therubbing-treated substrate, utilizing surfactants containing apolymerizable thiophene group as a hydrophobic group.

The above mesostructured film was immersed in diethylether solution ofiron chloride for 1 minute at room temperature to polymerize thethiophene group of the surfactant. In the ultraviolet-visible absorptionspectra of the mesostructured film obtained before and after theimmersion, a broad absorption at 500 nm was observed only in thespectrum after the immersion, thereby confirming the polymerizationreaction of the surfactant molecules. Formation of polythiophene in thepores was thus confirmed. The polarized absorption of the mesostructuredsilica film showed the anisotropy. This fact confirmed orientationcontrol of the polymer chain in the pores and orientation control of theconjugated polymer chains on a macroscopic scale.

Example 9

In this example, a mesostructured silica film having uniaxially orientedtubular pores was prepared by a sol-gel (spin coating) method on therubbing-treated substrate as in Example 1 and a cationic surfactantcontaining a pyrrole group, and the surfactant was subjected to achemical oxidation polymerization in the pores to form oriented polymerchains of a conjugated polymer.

A cationic surfactant D employed in the present example had a structureshown in FIG. 5D.

1.6 g of the cationic surfactant D was dissolved in 20 g of ethanol, and4.2 g of tetraethoxysilane was added. 0.27 g of water and 0.8 g of 0.1 Mhydrochloric acid were added to this solution and stirred for 2 hours toobtain a precursor solution.

This solution was applied on the rubbing-treated substrate by spincoating. The spin coating was conducted with a revolution speed of 2,000rpm and a rotation time of 20 seconds. The prepared film was dried in anenvironment at a temperature of 25° C. and a relative humidity of 50%.The obtained film was completely transparent.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of hexagonal porous structurescorresponding to a plane interval of 4.10 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of the uniaxial orientation of the tubularpores in this mesostructured silica film, the film was analyzed byin-plane X-ray diffraction. As a result, it was indicated that the poresin the prepared film were oriented parallel to the rubbing direction,and the distribution of the orientation direction was about 13° from thefull width of the half maximum of the diffraction peak in the in-planerocking curve.

Based on the foregoing, it was shown that a mesostructured silica filmhaving tubular pores of a uniaxial orientation was formed on therubbing-treated substrate, utilizing surfactants containing apolymerizable pyrrole group as a hydrophobic group.

The above mesostructured film was immersed in a solution of ironchloride in diethylether for 1 minute at room temperature to polymerizethe pyrrole group of the surfactant. In an ultraviolet-visible-nearinfrared absorption spectra of the mesostructured film obtained beforeand after the immersion, a broad absorption at 1,000 nm was observedonly in the spectrum after the immersion, thereby confirming thepolymerization reaction of the surfactant molecules. Formation ofpolypyrrole in the pores was thus confirmed. An investigation of thepolarizing characteristics of the observed absorption indicated that thepolarization direction of absorption was confirmed to be parallel to therubbing direction, namely along the direction of the oriented pores,thereby confirming orientation control of the polymer chain in the poresand orientation control of the conjugated polymer chains on amacroscopic scale.

Example 10

In this example, a mesostructured silica film having uniaxially orientedtubular pores was prepared by a sol-gel (mist coating) method on therubbing-treated substrate as in Example 1 and a cationic surfactantcontaining a pyrrole group, and the surfactant was subjected to achemical oxidation polymerization in the pores to form oriented polymerchains of a conjugated polymer.

The cationic surfactant D employed in the present example had astructure shown in FIG. 5D.

1.6 g of the cationic surfactant D was dissolved in 20 g of ethanol, and4.2 g of tetraethoxysilane was added. 0.27 g of water and 0.8 g of 0.1 Mhydrochloric acid were added to this solution and stirred for 2 hours toobtain a precursor solution.

The precursor solution was applied on the rubbing-treated substrate bymist coating, and the prepared film was dried in an environment at atemperature of 25° C. and a relative humidity of 50%. The obtained filmwas completely transparent.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of hexagonal porous structurescorresponding to a plane interval of 4.12 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of the uniaxial orientation of the tubularpores in this mesostructured silica film, this film was analyzed byin-plane X-ray diffraction. As a result, it was indicated that the poresin the prepared film were oriented parallel to the rubbing direction,and the distribution of the orientation direction was about 14° from thefull width of the half maximum of the diffraction peak in the in-planerocking curve.

Based on the foregoing, it was shown that a mesostructured silica filmhaving tubular pores of a uniaxial orientation was formed on therubbing-treated substrate, utilizing surfactants containing apolymerizable pyrrole group as a hydrophobic group.

The above mesostructured film was immersed in a diethylether solution ofiron chloride for 1 minute at room temperature to polymerize the pyrrolegroup of the surfactant. In ultraviolet-visible-near infrared absorptionspectra of the mesostructured film obtained before and after theimmersion, a broad absorption at 1,000 nm was observed only in thespectrum after the immersion, thereby confirming the polymerizationreaction of the surfactant molecules. Formation of polypyrrole in thepores was thus confirmed. An investigation of the polarizingcharacteristics of the observed absorption indicated that thepolarization direction of absorption was confirmed to be parallel to therubbing direction, namely along the direction of the oriented pores,thereby confirming orientation control of the polymer chain in the poresand orientation control of the conjugated polymer chains on amacroscopic scale.

Example 11

In this example, a mesostructured silica film having uniaxially orientedtubular pores was prepared by a soft lithography method in an arbitraryposition on the rubbing-treated substrate as in Example 1 and asurfactant A employed in Examples 1 to 4, and the surfactant wassubjected to a thermal polymerization in the pores to form orientedpolymer chains of a conjugated polymer.

1.6 g of the cationic surfactant A was dissolved in 20 g of ethanol, and4.2 g of tetraethoxysilane was added. 0.27 g of water and 0.8 g of 0.1 Mhydrochloric acid were added to this solution and stirred for 2 hours toobtain a precursor solution.

The micromold made of polydimethylsiloxane was pressed on therubbing-treated substrate and the precursor solution was poured from theend of the mold, whereby the solution was introduced by capillary actioninto the mold. After standing for 5 hours, the mold was removed from thesubstrate to obtain the patterned mesostructured film.

After drying in the air, it was confirmed that a transparent film wasformed only in an area of coating by the soft lithography method.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of hexagonal porous structurescorresponding to a plane interval of 4.07 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of the uniaxial orientation of the tubularpores in this mesostructured silica film, the film was analyzed byin-plane X-ray diffraction. As a result, it was indicated that the poresin the prepared film were oriented perpendicular to the rubbingdirection, and the distribution of the orientation direction was about11° from the full width of the half maximum of the diffraction peak inthe in-plane rocking curve.

Based on the foregoing, it was shown that a patterned mesostructuredsilica film having tubular pores of a uniaxial orientation was formed onthe rubbing-treated substrate, utilizing surfactants containing apolymerizable diacetylene group as a hydrophobic group.

The above mesostructured film was heated for 3 hours at 170° C. in anitrogen gas atmosphere to polymerize the diacetylene group of thesurfactant. Infrared absorption spectroscopy of the mesostructured filmwas performed by an ATR method before and after heating. As a result, astrong absorption band of an acetylene bond at 2,260 cm⁻¹ observedbefore heating vanished after the heating, while other peaks did notshow a change. This result confirmed that the polymerization of thesurfactant molecules took place without decomposition of the surfactantmolecules. Also, fluorescence, which was not observed in the film beforeheating, was observed in the film after the heating, thus confirmingformation of polydiacetylene in the pore. An investigation of thepolarizing characteristics of the observed fluorescence indicated thatthe polarization direction of fluorescence was confirmed to beperpendicular to the rubbing direction, namely along the direction ofthe oriented pores, thereby confirming orientation control of thepolymer chain in the pores and orientation control of the conjugatedpolymer chains on a macroscopic scale.

Example 12

In this example, a mesostructured silica film having uniaxially orientedtubular pores was prepared by a pen lithography method in an arbitraryposition on the rubbing-treated substrate as in Example 1 and asurfactant A employed in Examples 1 to 4, and was subjected to a thermalpolymerization in the pores to form oriented polymer chains of aconjugated polymer.

1.6 g of the cationic surfactant A was dissolved in 20 g of ethanol, and4.2 g of tetraethoxysilane was added. 0.27 g of water and 0.8 g of 0.1 Mhydrochloric acid were added to this solution and stirred for 2 hours toobtain a precursor solution.

The solution was patterned on the rubbing-treated substrate by a penlithography method, and the prepared film was dried in the air at roomtemperature. The pen lithography was conducted under conditions of a penorifice of 50.0 μm, a stage speed of 2.5 cm/s and a fluid supply rate of4.0 cm.

By observing the substrate after drying in air, it was confirmed that atransparent film was formed only in an area of coating by the penlithography method.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of hexagonal porous structurescorresponding to a plane interval of 4.09 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of the uniaxial orientation of the tubularpores in this mesostructured silica film, this film was analyzed byin-plane X-ray diffraction. As a result, it was indicated that the poresin the prepared film were oriented perpendicular to the rubbingdirection, and the distribution of the orientation direction was about10° from the full width of the half maximum of the diffraction peak inthe in-plane rocking curve.

Based on the foregoing, it was shown that a patterned mesostructuredsilica film having tubular pores of a uniaxial orientation was formed onthe rubbing-treated substrate, utilizing surfactants containing apolymerizable diacetylene group as a hydrophobic group.

The above mesostructured film was heated for 3 hours at 170° C. in anitrogen gas atmosphere to polymerize the diacetylene group of thesurfactant. Infrared absorption spectroscopy of the mesostructured filmwas performed by an ATR method before and after heating. As a result, astrong absorption band of an acetylene bond at 2,260 cm⁻¹ observedbefore heating vanished after the heating, while other peaks did notshow a change. This result confirmed that the polymerization of thesurfactant molecules took place without decomposition of the surfactantmolecules. Also, fluorescence, which was not observed in the film beforeheating, was observed in the film after the heating, thus confirmingformation of polydiacetylene in the pores. An investigation of thepolarizing characteristics of the observed fluorescence indicated thatthe polarization direction of fluorescence was confirmed to beperpendicular to the rubbing direction, namely along the direction ofthe oriented pores, thereby confirming orientation control of thepolymer chain in the pores and orientation control of the conjugatedpolymer chains on a macroscopic scale.

Example 13

In this example, a mesostructured silica film having uniaxially orientedtubular pores was prepared by an ink jet method in an arbitrary positionon the rubbing-treated substrate as in Example 1 and a surfactant Aemployed in Examples 1 to 4, and was subjected to a thermalpolymerization in the pores to form oriented polymer chains of aconjugated polymer.

1.6 g of the cationic surfactant A was dissolved in 20 g of ethanol, and4.2 g of tetraethoxysilane was added. 0.27 g of water and 0.8 g of 0.1 Mhydrochloric acid were added to this solution and stirred for 2 hours toobtain a precursor solution.

The solution was applied on the rubbing-treated substrate by an ink jetmethod in a pattern, and the prepared film was dried in air at roomtemperature.

By observing the substrate after drying in air, it was confirmed that atransparent film was formed only in an area formed by the ink jetmethod.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of hexagonal porous structurescorresponding to a plane interval of 4.12 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of the uniaxial orientation of the tubularpores in this mesostructured silica film, this film was analyzed byin-plane X-ray diffraction. As a result, it was indicated that the poresin the prepared film were oriented perpendicular to the rubbingdirection, and the distribution of the orientation direction was about12° from the full width of the half maximum of the diffraction peak inthe in-plane rocking curve.

Based on the foregoing, it was shown that a mesostructured silica filmhaving tubular pores of a uniaxial orientation was formed on therubbing-treated substrate, utilizing surfactants containing apolymerizable diacetylene group as a hydrophobic group.

The above mesostructured film was heated for 3 hours at 170° C. in anitrogen gas atmosphere to polymerize the diacetylene group of thesurfactant. Infrared absorption spectroscopy of the mesostructured filmwas performed by an ATR method before and after heating. As a result, astrong absorption band of an acetylene bond at 2,260 cm⁻¹ observedbefore heating vanished after the heating, while other peaks did notshow a change. This result confirmed that the polymerization of thesurfactant molecules took place without decomposition of the surfactantmolecules. Also, fluorescence, which was not observed in the film beforeheating, was observed in the film after the heating, thus confirmingformation of polydiacetylene in the pores. An investigation of thepolarizing characteristics of the observed fluorescence indicated thatthe polarization direction of fluorescence was confirmed to beperpendicular to the rubbing direction, namely along the direction ofthe oriented pores, thereby confirming orientation control of thepolymer chain in the pores and orientation control of the conjugatedpolymer chains on a macroscopic scale.

Comparative Example

An ethanol solution of tin tetrachloride and the nonionic surfactant Bwas prepared in the same manner as in Example 5, and this precursorsolution was applied by dip coating on an isotropic silica glasssubstrate without coating or particular processing on the surface.

The coated substrate was dried, as in Example 5, for 10 hours in anenvironment at a temperature of 40° C. and a relative humidity of 20%,then maintained for 40 hours in an environment at a temperature of 40°C. and a relative humidity of 80%, and the relative humidity was thenreduced to 20%. The obtained film was completely transparent.

X-ray diffraction analysis of this film confirmed a strong diffractionpeak assigned to the (100) plane of hexagonal porous structurescorresponding to a plane interval of 4.60 nm, thereby confirming thatthe film had a pore structure in which tubular pores are hexagonallypacked.

For a quantitative evaluation of the uniaxial orientation of the tubularpores in this mesostructured tin oxide film, this film was analyzed byin-plane X-ray diffraction. As a result, the orientation state of thepores in the prepared film was completely isotropic and no increase inthe X-ray diffraction intensity in a particular direction was observed.

The above mesostructured tin oxide film was heated for 3 hours at 170°C. in a nitrogen gas atmosphere to polymerize the diacetylene group ofthe surfactant. It was indicated by X-ray diffraction analysis that thepore structures shrank in a period thereof, but retained the porestructure by heating. Infrared absorption spectroscopy of themesostructured film was performed by an ATR method before and afterheating. As a result, a strong absorption band of an acetylene bond at2,260 cm⁻¹ observed before heating vanished after the heating, whileother peaks did not show a change. This result confirmed that thepolymerization of the surfactant molecules took place withoutdecomposition of the surfactant molecules. Also, fluorescence, which wasnot observed in the film before heating, was observed in the film afterthe heating, thus confirming formation of polydiacetylene in the pores.In an investigation of the polarizing characteristics of the observedfluorescence, dependence on polarization was not observed in theintensity of the fluorescence, thus confirming that any specificorientation was absent in the polymer chains.

As described above, according to the present invention, themesostructured film having tubular pores of a uniaxial orientation canbe formed on the substrate with surface anisotropy, utilizingpolymerizable surfactants. Further, by polymerizing the surfactant inthe uniaxially oriented pores, a structure in which conjugated polymersare oriented in one direction can be obtained.

1. A method for producing a structured material comprising steps of:providing a substrate showing anisotropy on a surface; then bringing thesurface of the substrate into contact with a solution comprising asurfactant, which has a functional group for polymerization in amolecular structure, a solvent therefor, and a matrix raw material,which can form a matrix by hydrolysis and condensation; and maintainingthe contact for a predetermined time to form the matrix on the surfaceand to assemble the surfactant in the matrix in a predetermineddirection based on the anisotropy of the substrate.
 2. The methodaccording to claim 1, wherein said surfactant has a diacetylene,thiophene, or pyrrole group in the molecular structure.
 3. The methodaccording to claim 1, wherein, in said maintaining step, the substrateis exposed to water vapor.
 4. The method according to claim 1, furthercomprising a step of polymerizing the surfactant after the maintainingstep.
 5. The method according to claim 4, wherein said polymerizing stepis executed by thermal polymerization, photopolymerization, or chemicalpolymerization.